CN113731455B - Desulfurization catalyst with hydrogen production function, preparation method thereof and hydrocarbon oil desulfurization method - Google Patents
Desulfurization catalyst with hydrogen production function, preparation method thereof and hydrocarbon oil desulfurization method Download PDFInfo
- Publication number
- CN113731455B CN113731455B CN202010464534.5A CN202010464534A CN113731455B CN 113731455 B CN113731455 B CN 113731455B CN 202010464534 A CN202010464534 A CN 202010464534A CN 113731455 B CN113731455 B CN 113731455B
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- China
- Prior art keywords
- catalyst
- moc
- hydrocarbon oil
- slurry
- desulfurization
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 119
- 230000023556 desulfurization Effects 0.000 title claims abstract description 119
- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 95
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 95
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000001257 hydrogen Substances 0.000 title claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 34
- 239000011230 binding agent Substances 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 90
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 84
- 239000002002 slurry Substances 0.000 claims description 63
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 229910052717 sulfur Inorganic materials 0.000 claims description 39
- 239000011593 sulfur Substances 0.000 claims description 39
- 238000002156 mixing Methods 0.000 claims description 37
- 239000011787 zinc oxide Substances 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 23
- 229910021641 deionized water Inorganic materials 0.000 claims description 23
- 239000012018 catalyst precursor Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 230000003009 desulfurizing effect Effects 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 6
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 claims description 5
- 238000002441 X-ray diffraction Methods 0.000 claims description 5
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
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- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- MODMKKOKHKJFHJ-UHFFFAOYSA-N magnesium;dioxido(dioxo)molybdenum Chemical compound [Mg+2].[O-][Mo]([O-])(=O)=O MODMKKOKHKJFHJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001228 spectrum Methods 0.000 claims 1
- 239000003502 gasoline Substances 0.000 abstract description 51
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 19
- 150000004706 metal oxides Chemical class 0.000 abstract description 19
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 14
- 239000000203 mixture Substances 0.000 description 46
- 238000003756 stirring Methods 0.000 description 29
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 22
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- 238000001354 calcination Methods 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 14
- 238000001694 spray drying Methods 0.000 description 14
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 13
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- 235000012211 aluminium silicate Nutrition 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
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- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
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- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
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- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
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- 239000005909 Kieselgur Substances 0.000 description 3
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 3
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
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- 238000000227 grinding Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229910052901 montmorillonite Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 2
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- 238000001556 precipitation Methods 0.000 description 2
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- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
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- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
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- 238000004438 BET method Methods 0.000 description 1
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
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- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
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- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
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- 235000011009 potassium phosphates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
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- -1 rectorite Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 229910052624 sepiolite Inorganic materials 0.000 description 1
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- 239000004317 sodium nitrate Substances 0.000 description 1
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- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
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- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
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- 150000004684 trihydrates Chemical class 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
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Abstract
The invention relates to a desulfurization catalyst with hydrogen production function, which comprises the following components by taking the total weight of the desulfurization catalyst as a reference: 1) 10 to 80 wt% of at least one metal oxide selected from the group consisting of group IIB, VB and VIB elements; 2) 3 to 35 wt% of an alumina binder; 3) 5 to 40 wt% of alpha-MoC; 4) 5 to 30 wt% of a metal promoter selected from at least one of cobalt, nickel, iron and manganese. The invention also provides a preparation method of the desulfurization catalyst and a hydrocarbon oil desulfurization method. In the desulfurization catalyst provided by the invention, alpha-MoC interacts with active metal to promote dehydroaromatization of naphthenes, realize high-depth desulfurization, improve the octane number of gasoline, produce hydrogen and reduce the hydrogen consumption in the desulfurization process.
Description
Technical Field
The invention relates to the field of hydrocarbon oil desulfurization, in particular to a hydrocarbon oil desulfurization catalyst, a preparation method thereof and a hydrocarbon oil desulfurization method.
Background
With increasing emphasis on environmental protection, environmental regulations are becoming more stringent, and reducing sulfur content in gasoline and diesel is considered one of the most important measures to improve air quality. Most of the sulfur in our gasoline products comes from hot processed gasoline blending components, such as catalytically cracked gasoline. Therefore, the reduction of the sulfur content in the hot-processed gasoline is beneficial to reducing the sulfur content of gasoline products in China. The current gasoline product standard GB 17930-2016 "automotive gasoline" in China requires that national V gasoline quality standard with sulfur mass fraction not more than 10mg/kg be implemented nationally in 2017. China will implement national VIA gasoline standard in 2019 1 month, and the required olefin content is not higher than 18%, and comprehensively implement national VIB gasoline quality standard in 2023 1 month, and the required olefin content is not higher than 15%. In this case, the catalytically cracked gasoline must undergo deep desulfurization while the olefin content needs to be reduced to make the gasoline product meet environmental requirements.
At present, the deep desulfurization method of the oil products mainly comprises two methods of selective catalytic hydrodesulfurization and catalytic hydrogenation adsorption desulfurization. The catalytic hydrogenation adsorption desulfurization realizes the adsorption removal of sulfides in hydrocarbon oil under certain temperature, pressure and hydrogen conditions, and the technology has the characteristics of low hydrogen consumption and low requirement on the purity of hydrogen, so that the technology has wide application prospect in the aspect of fuel oil desulfurization.
CN1355727a discloses an adsorbent composition suitable for removing sulfur from cracked-gasoline and diesel fuels, consisting of zinc oxide, silicon oxide, aluminum oxide and nickel, wherein the nickel is present in a substantially reduced valence state in an amount that is capable of removing sulfur from a cracked-gasoline or diesel fuel stream contacted with the nickel-containing adsorbent composition under desulfurization conditions. The composition is obtained by granulating a mixture of zinc oxide, silicon oxide and aluminum oxide to form granules, drying, calcining, impregnating with nickel or a nickel-containing compound, drying, calcining, and reducing.
CN1382071a discloses an adsorbent composition suitable for removing sulfur from cracked-gasoline and diesel fuels, consisting of zinc oxide, silicon oxide, aluminum oxide and cobalt, wherein the cobalt is present in a substantially reduced valence state in an amount effective to remove sulfur from a cracked-gasoline or diesel fuel stream contacted with the cobalt-containing adsorbent composition under desulfurization conditions.
US6150300 discloses a method of preparing an adsorbent comprising preparing spherical particles: (a) Mixing a silica-containing composition, a composition containing a metal oxide dispersed in an aqueous medium, and a composition containing zinc oxide to form a first mixture without extruding the first mixture; (b) The first mixture is formed into spheres having a diameter of 10-1000 mm. Wherein step (a) further comprises mixing with a metal promoter.
CN1422177a discloses an adsorbent composition suitable for removing sulfur from cracked-gasoline and diesel fuels, consisting of zinc oxide, expanded perlite, alumina and promoter metal, wherein the promoter metal is present in a substantially reduced valence state and in an amount that will remove sulfur from the cracked-gasoline or diesel fuel stream when contacted therewith under desulfurization conditions.
CN1627988A discloses a sorbent composition suitable for removing elemental sulfur and sulfur compounds from cracked-gasoline and diesel fuel, said sorbent composition comprising: zinc oxide, expanded perlite, aluminate, and promoter metal, wherein the promoter metal is present in an amount that will result in desulfurization from a stream of cracked-gasoline or diesel fuel when the cracked-gasoline or diesel fuel stream is contacted therewith under desulfurization conditions, and at least a portion of the promoter metal is present in the 0-valent state.
CN1856359a discloses a method of producing a composition comprising: a) Mixing the liquid, the zinc-containing compound, the silica-containing material, alumina, and the promoter to form a mixture thereof; b) Drying the mixture to form a dried mixture; c) Calcining the dried mixture to form a calcined mixture; d) Reducing the calcined mixture with a suitable reducing agent under suitable conditions to produce a composition having a reduced valence cocatalyst content therein, and e) recovering the composition. The promoter comprises a plurality of metals selected from nickel and the like.
CN1871063a discloses a method of producing a composition, the method comprising: a) Mixing a liquid, a zinc-containing compound, a silica-containing material, and alumina to form a mixture thereof; b) Drying the mixture to form a first dried mixture; c) Calcining the first dried mixture to form a first calcined mixture; d) Incorporating a promoter into or onto the first calcined mixture to form a promoted mixture; e) Contacting the promoted mixture with an acid selected from citric acid, tartaric acid, and combinations thereof to form a contacted mixture; f) Drying the contacted mixture to form a second dried mixture; g) Calcining the second dried mixture to form a second calcined mixture; h) Reducing the second calcined mixture with a suitable reducing agent under suitable conditions to produce a composition having reduced valence promoter content therein, and i) recovering the composition.
Although the disclosed desulfurization catalyst has certain desulfurization performance, along with the improvement of the quality standard of gasoline, the sulfur content requirement of the product gasoline is also continuously strict, olefin is inevitably subjected to hydrogenation reaction during desulfurization, so that the octane number of the product gasoline is reduced, and the hydrogen consumption is increased. It is therefore desirable to provide a higher performance desulfurization catalyst that achieves high depth desulfurization while increasing the octane number of the product gasoline and reducing the hydrogen consumption during desulfurization.
Disclosure of Invention
The invention aims to overcome the defects that octane number loss and hydrogen consumption increase are caused during desulfurization of an adsorbent in the prior art, and provides a hydrocarbon oil desulfurization catalyst with a hydrogen production function, a preparation method thereof and a hydrocarbon oil desulfurization method.
The hydrocarbon oil desulfurization catalyst provided by the invention can promote the dehydroaromatization of naphthenes, improve the octane number of gasoline while realizing high-depth desulfurization, also can produce hydrogen, and reduce the hydrogen consumption in the desulfurization process.
The invention provides a hydrocarbon oil desulfurization catalyst with hydrogen production function, which comprises the following components by taking the total weight of the hydrocarbon oil desulfurization catalyst as a reference: 1) 10 to 80 wt% of at least one metal oxide selected from the group consisting of group IIB, VB and VIB elements; 2) 3 to 35 wt% of alumina; 3) 5 to 40 wt% of alpha-MoC; 4) 5 to 30 wt% of a metal promoter selected from at least one of cobalt, nickel, iron and manganese.
The invention also provides a method for preparing the hydrocarbon oil desulfurization catalyst, which comprises the following steps:
(1) Dissolving molybdate in de-solventEvaporating in ion water to remove water, drying, and calcining to obtain MoO 3 A solid; the obtained MoO 3 Carbonizing the solid in a carbonization atmosphere containing a carbon source and hydrogen at the same time to obtain alpha-MoC;
(2a) Contacting alpha-MoC, an alumina binder, water and an acidic liquid to form a slurry, and mixing the slurry with at least one metal oxide selected from the group consisting of group IIB, VB and VIB elements to obtain a carrier slurry; or alternatively
(2b) Contacting an alumina binder, water and an acidic liquid to form a slurry, and mixing the slurry with at least one metal oxide selected from the group consisting of group IIB, VB and VIB elements, α -MoC to obtain a carrier slurry;
(3) Molding, first drying and first roasting the carrier slurry to obtain a carrier;
(4) Introducing a precursor of a metal promoter into the carrier, and then performing second drying and second roasting to obtain a catalyst precursor;
(5) And reducing the catalyst precursor in a hydrogen atmosphere to obtain the hydrocarbon oil desulfurization catalyst.
The invention also provides a hydrocarbon oil desulfurization catalyst prepared by the method.
The invention also provides a method for desulfurizing hydrocarbon oil, which comprises the following steps: under the hydrogen atmosphere, sulfur-containing hydrocarbon oil and the hydrocarbon oil desulfurization catalyst provided by the invention are subjected to desulfurization reaction at 350-500 ℃ and 0.5-4 MPa.
The composition of the hydrocarbon oil desulfurization catalyst provided by the invention contains alpha-MoC, can interact with an active metal accelerator, can more effectively adsorb sulfur in hydrocarbon oil to the hydrocarbon oil desulfurization catalyst in the hydrocarbon oil desulfurization process to obtain hydrocarbon oil with lower sulfur content, can also improve the octane number of gasoline, can also produce hydrogen, and reduces the hydrogen consumption in the desulfurization process. .
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate the invention and together with the description serve to explain, without limitation, the invention. In the drawings:
FIG. 1 is an XRD pattern of a hydrocarbon oil desulfurization catalyst A1 obtained in example 1;
fig. 2 is an XRD pattern of the hydrocarbon oil desulfurization catalyst B1 obtained in comparative example 1.
Detailed Description
The following describes specific embodiments of the present invention in detail. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a hydrocarbon oil desulfurization catalyst, which comprises the following components by taking the total weight of the hydrocarbon oil desulfurization catalyst as a reference: 1) 10 to 80 wt% of at least one metal oxide selected from the group consisting of group IIB, VB and VIB elements; 2) 3 to 35 wt% of an alumina binder; 3) 5 to 40 wt% of alpha-MoC; 4) 5 to 30 wt% of a metal promoter selected from at least one of cobalt, nickel, iron and manganese.
Preferably, the hydrocarbon oil desulfurization catalyst comprises, based on the total weight of the hydrocarbon oil desulfurization catalyst: 25 to 70 weight percent of the metal oxide, 6 to 25 weight percent of the alumina binder, 7 to 30 weight percent of the alpha-MoC, and 8 to 25 weight percent of the metal promoter.
More preferably, the hydrocarbon oil desulfurization catalyst comprises, based on the total weight of the hydrocarbon oil desulfurization catalyst: 40 to 60 weight percent of the metal oxide, 8 to 15 weight percent of the alumina binder, 10 to 25 weight percent of the alpha-MoC and 12 to 20 weight percent of the metal accelerator.
In the invention, the content of each component in the hydrocarbon oil desulfurization catalyst can be determined by an XRD crystal phase analysis method. According to the invention, in a spectrogram obtained by XRD analysis of the hydrocarbon oil desulfurization catalyst, crystal phase peaks of alpha-MoC exist at 2 theta of 2 theta=39.6 DEG, 52.2 DEG and 62.5 deg.
Wherein the average particle diameter of the alpha-MoC is 1 to 50nm, preferably 5 to 40nm, more preferably 10 to 35nm. Specific surface area of alpha-MoC of 5m 2 /g～200m 2 /g, preferably 10m 2 /g～150m 2 Preferably 20 to 80m 2 And/g. In the present invention, the average particle diameter of the. Alpha. -MoC is 5 to 40nm, preferably 10 to 30nm. Specific surface area of alpha-MoC 10m 2 /g～100m 2 /g, preferably 30m 2 /g～60m 2 /g。
According to the present invention, the at least one metal oxide selected from the group consisting of group IIB, VB and VIB elements may be at least one of zinc oxide, cadmium oxide, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, preferably at least one of zinc oxide, molybdenum oxide and vanadium oxide; more preferably, the metal oxide is zinc oxide.
According to the present invention, preferably, when the metal promoter is nickel and/or cobalt, the hydrocarbon oil desulfurization catalyst may have high desulfurization activity and regeneration performance; it may be further preferred that the metal promoter is nickel.
According to the present invention, preferably, the alumina is at least one of γ -alumina, η -alumina, θ -alumina and χ -alumina; preferably, the alumina is gamma-alumina.
In the present invention, the hydrocarbon oil desulfurization catalyst may further contain other components such as components that the desulfurization catalyst may contain, for example, layered clay, alkali metal oxide, and the like. Wherein the amount of the pillared clay may be 1 to 10% by weight, the amount of the clay may be 1 to 10% by weight, and the amount of the alkali metal oxide may be 0.1 to 5% by weight. Wherein, the layer column clay is interlayer mineral crystal and is formed by regularly and alternately arranging two single-layer mineral clay components, and the distance between the bottom surfaces is not less than 1.7nm. Examples of preferred pillared clays include, but are not limited to, at least one of rectorite, yun Mengdan, bentonite, montmorillonite, and smectite. Wherein the clay may be selected from clay raw materials well known to those skilled in the art, and common clay types may be used in the present invention, preferably the clay may be selected from one or more of kaolin, halloysite, montmorillonite, diatomaceous earth, halloysite, quasi halloysite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and bentonite. Wherein the alkali metal oxide may be sodium oxide and/or potassium oxide.
The invention also provides a method for preparing the hydrocarbon oil desulfurization catalyst, which comprises the following steps:
(1) Dissolving molybdate in deionized water, evaporating to remove water, drying, and roasting to obtain MoO 3 A solid; the obtained MoO 3 Carbonizing the solid in a carbonization atmosphere containing a carbon source and hydrogen to obtain alpha-MoC;
(2a) Contacting alpha-MoC, an alumina binder, water and an acidic liquid to form a slurry, and mixing the slurry with at least one metal oxide selected from the group consisting of group IIB, VB and VIB elements to obtain a carrier slurry; or alternatively
(2b) Contacting an alumina binder, water and an acidic liquid to form a slurry, and mixing the slurry with at least one metal oxide selected from the group consisting of group IIB, VB and VIB elements, α -MoC to obtain a carrier slurry;
(3) Molding, first drying and first roasting the carrier slurry to obtain a carrier;
(4) Introducing a precursor of a metal promoter into the carrier, and then drying and roasting to obtain a catalyst precursor;
(5) And reducing the catalyst precursor in a hydrogen atmosphere to obtain the hydrocarbon oil desulfurization catalyst.
According to the invention, in step (1), the molybdate may be selected from sodium molybdate Na 2 MoO 4 Magnesium molybdate MgMoO 4 Ammonium heptamolybdate ([ NH) 4 ] 6 Mo 7 O 24 ·4H 2 O), preferably ammonium heptamolybdate ([ NH ] 4 ] 6 Mo 7 O 24 ·4H 2 O) the mass concentration of the molybdate water solution can be 1 to 20 percent, and the best is5 to 15 percent of the total weight of the plant.
The drying method and conditions in step (1) are well known to those skilled in the art, and for example, the drying method may be air drying, oven drying, air drying. Preferably, the temperature of the second step may be from room temperature to 300 ℃, preferably from 50 to 100 ℃; the drying time is 0.5 to 100 hours, preferably 2 to 20 hours.
The calcination conditions in step (1) are also well known to those skilled in the art, and preferably the calcination temperature is 400 to 700 ℃, preferably 450 to 650 ℃; the calcination time is 0.5 to 100 hours, more preferably 0.5 to 10 hours.
The carbonization atmosphere may be CH 4 /H 2 Or C 2 H 6 /H 2 The volume ratio of the carbon source to the hydrogen source is 10-30%, preferably 15-25%, the temperature rise speed of carbonization program is 1-10 ℃/min, the carbonization temperature is 400-800 ℃, preferably 500-700 ℃, and the carbonization time is 60-400min, preferably 100-300 min.
The alpha-MoC prepared in the step (1) has a face centered cubic (fcc) structure, has strong interaction with a metal accelerator, can realize dehydroaromatization of naphthenes, and improves the octane number of the gasoline product while realizing desulfurization.
Wherein the average particle diameter of the alpha-MoC is 1 to 50nm, preferably 5 to 40nm, more preferably 10 to 35nm. Specific surface area of alpha-MoC of 5m 2 /g～200m 2 /g, preferably 10m 2 /g～150m 2 Preferably 20 to 80m 2 /g。
In the present invention, the at least one metal oxide selected from the group consisting of group IIB, VB and VIB elements may be at least one of zinc oxide, cadmium oxide, vanadium oxide, niobium oxide tantalum oxide, chromium oxide and; preferably at least one of zinc oxide and vanadium oxide; more preferably zinc oxide. The metal oxide may be added in the form of powder of the metal oxide, or may be added in the form of slurry after mixing the metal oxide with water to form a slurry.
According to the invention, the alumina binder may be alumina or converted to gamma-Al under the first firing conditions 2 O 3 Is a substance of (a). Preferably, the alumina binder may be selected from at least one of SB powder, hydrated alumina, alumina sol, boehmite (boehmite), pseudo-boehmite (pseudo-boehmite), alumina trihydrate and amorphous aluminum hydroxide; preferably, the alumina binder is at least one of SB powder, pseudo-boehmite, and alumina sol.
According to the present invention, the acidic liquid may be an acid or an aqueous solution of an acid, which may be selected from a water-soluble inorganic acid and/or an organic acid, preferably the acid may be at least one of hydrochloric acid, nitric acid, phosphoric acid and acetic acid.
According to the invention, the acidic liquid is preferably used in an amount such that the pH of the carrier slurry is between 1 and 5, preferably between 1.5 and 4.
In the present invention, the amount of water added in steps (2 a) and (2 b) is not particularly limited as long as the carrier slurry can be obtained. For example, the weight ratio of the amount of water added to the alumina binder is 5:1 to 10:1, a step of; or the weight ratio of the amount of water added to the sum of the weight of the alumina binder and the α -MoC is 5:1 to 10:1.
in the present invention, other components for preparing a desulfurization catalyst, such as a layered clay, a precursor of an alkali metal oxide, etc., may be further added to the steps (2 a) and (2 b). The layered clay is as described above and will not be described again. The precursor of the alkali metal oxide may be a substance that is converted into the alkali metal oxide under the first firing conditions of step (2), such as an alkali metal oxide, an alkali metal nitrate, an alkali metal sulfate, an alkali metal phosphate, for example, may be selected from one or a combination of several of sodium oxide, potassium oxide, sodium nitrate, potassium sulfate, sodium sulfate, potassium phosphate, and sodium phosphate.
In the present invention, the carrier slurry obtained may be in the form of a paste or slurry, or the like. The carrier slurry may be dried and reshaped after thickening. More preferably, the carrier slurry is in the form of a slurry, and the forming can be achieved by spray drying to form microspheres having a particle size of 20-200 microns. For ease of spray drying, the solids content of the carrier slurry prior to drying may be from 10 to 50% by weight, preferably from 20 to 50% by weight. The process of obtaining the carrier slurry may further include adding water, and the amount of water to be added is not particularly limited as long as the obtained carrier slurry satisfies the above-mentioned solid content.
In the present invention, the first drying method and conditions in step (3) are well known to those skilled in the art, and for example, the drying method may be air drying, oven drying, or air drying. Preferably, the temperature of the first drying may be between room temperature and 400 ℃, preferably between 100 and 350 ℃; the first drying time is 0.5 hours or more, preferably 0.5 to 100 hours, and more preferably 2 to 20 hours.
In the present invention, the first calcination conditions in step (3) are also well known to those skilled in the art, and preferably the first calcination temperature is 400 to 700 ℃, preferably 450 to 650 ℃; the first calcination time is at least 0.5 hours, preferably 0.5 to 100 hours, more preferably 0.5 to 10 hours.
According to the invention, step (4) is used to add a metal promoter as previously indicated. The precursor of the metal accelerator is a substance which can be converted into an oxide of the metal accelerator under the second roasting condition; preferably, the precursor of the metal promoter may be selected from at least one of acetate, carbonate, nitrate, sulfate, thiocyanate, and oxide of the metal promoter. Preferably, the precursor of the metal promoter may be at least one of acetate, carbonate, nitrate, sulfate, thiocyanate and oxide of at least one of cobalt, nickel, iron and manganese; preferably nickel and/or cobalt, at least one of acetate, carbonate, nitrate, sulfate, thiocyanate and oxide; nickel nitrate and/or cobalt nitrate may be preferred; more preferably at least one of nickel acetate, carbonate, nitrate, sulfate, thiocyanate and oxide; nickel nitrate is particularly preferred.
According to the invention, the method of introducing the precursor of the metal promoter on the support is preferably impregnation or precipitation. The impregnation may be impregnation of the support with a solution or suspension of a precursor of the metal promoter; the precipitation may be by mixing a solution or suspension of the precursor of the metal promoter with the support and then adding ammonia to precipitate the precursor of the metal promoter on the support.
According to the present invention, the temperature of the second drying in step (4) is preferably 50 to 300 ℃, preferably 100 to 250 ℃; the second drying time is 0.5 to 8 hours, preferably 1 to 5 hours.
Preferably, the temperature of the second calcination in step (4) is 300-800 ℃, preferably 450-750 ℃; the second calcination time is 0.5 hours or more, preferably 1 to 3 hours. The second calcination may be performed in the presence of oxygen or an oxygen-containing gas until the volatile material is removed and the precursor of the metal promoter is converted to the oxide form of the metal promoter to give the catalyst precursor.
According to the present invention, in the step (5), the oxide of the metal promoter in the catalyst precursor is converted into a metal simple substance, and the catalyst precursor may be reduced in a hydrogen-containing atmosphere so that the metal promoter exists substantially in a reduced state, to obtain the catalyst of the present invention. The reducing conditions only convert the oxide of the metal promoter in the catalyst precursor to elemental metal, while the metal oxide in the support does not. Preferably, the temperature of the reduction is 300-600 ℃, preferably 400-500 ℃; the reduction time is 0.5-6 h, preferably 1-3 h; the hydrogen content in the hydrogen-containing atmosphere is 10 to 60% by volume.
In the present invention, the reduction of the catalyst precursor in the step (5) may be performed immediately after the preparation of the catalyst precursor, or may be performed before the use (i.e., before the desulfurization adsorption). Since the metal promoter is easily oxidized and the metal promoter in the catalyst precursor exists in the form of an oxide, it is preferable that the step (5) of reducing the catalyst precursor is performed before the desulfurization adsorption is performed for the convenience of transportation. The reduction is such that the metal in the oxide of the metal promoter is substantially present in a reduced state to give the desulfurization catalyst of the present invention.
According to the present invention, the alumina binder, α -MoC, the metal oxide and the precursor of the metal promoter are preferably added in such amounts that the hydrocarbon oil desulfurization catalyst obtained contains 10 to 80 wt% of the metal oxide, preferably 25 to 70 wt%, more preferably 40 to 60 wt%, based on the total weight of the hydrocarbon oil desulfurization catalyst; 3 to 35 wt% of alumina, preferably 6 to 25 wt%, more preferably 8 to 15 wt%; from 5 to 40% by weight of alpha-MoC, preferably from 10 to 30% by weight, more preferably from 12 to 25% by weight; the metal promoter is contained in an amount of 5 to 30% by weight, preferably 8 to 25% by weight, more preferably 12 to 20% by weight.
The method provided by the invention can be added with other components in an amount that the obtained hydrocarbon oil desulfurization catalyst contains 1-10 wt% of layer column clay, 1-10 wt% of clay and 0.1-5 wt% of alkali metal oxide.
The invention also provides a hydrocarbon oil desulfurization catalyst prepared by the method.
The invention also provides a method for desulfurizing hydrocarbon oil, which comprises the following steps: under the hydrogen atmosphere, sulfur-containing hydrocarbon oil and the hydrocarbon oil desulfurization catalyst provided by the invention are subjected to desulfurization reaction at 350-500 ℃ and 0.5-4 MPa; preferably, the desulfurization reaction is carried out at 400 to 450 ℃ and 1.0 to 2.0 MPa. In this process sulfur in the hydrocarbon oil is adsorbed onto the catalyst, resulting in a hydrocarbon oil with a low sulfur content.
In the invention, the catalyst after the reaction can be reused after regeneration. The regeneration is carried out under an oxygen atmosphere, and the conditions of the regeneration include: the pressure of regeneration is normal pressure, the temperature of regeneration is 400-700 ℃, and the preferable temperature is 500-600 ℃.
In the invention, the regenerated catalyst needs to be reduced in the atmosphere containing hydrogen before the hydrocarbon oil is desulfurized again, and the reduction conditions of the regenerated catalyst comprise: the temperature is 350-500 ℃, preferably 400-450 ℃; the pressure is 0.2 to 2MPa, preferably 0.2 to 1.5MPa.
In the present invention, the hydrocarbon oil includes cracked gasoline and diesel fuel, wherein "cracked gasoline" means hydrocarbons having a boiling range of 40 ℃ to 210 ℃ or any fraction thereof, which is a product from a thermal or catalytic process that cracks larger hydrocarbon molecules into smaller molecules. Suitable thermal cracking processes include, but are not limited to, coking, thermal cracking, visbreaking, and the like, and combinations thereof. Examples of suitable catalytic cracking processes include, but are not limited to, fluid catalytic cracking and heavy oil catalytic cracking, among others, and combinations thereof. Thus, suitable catalytically cracked gasolines include, but are not limited to, coker gasolines, thermally cracked gasolines, visbreaker gasolines, fluid catalytic cracked gasolines, and heavy oil cracked gasolines, and combinations thereof. In some cases, the cracked-gasoline may be fractionated and/or hydrotreated prior to desulfurization when used as a hydrocarbon-containing fluid in the process of the present invention. By "diesel fuel" is meant a liquid composed of a mixture of hydrocarbons having a boiling range of 170 ℃ to 450 ℃ or any fraction thereof. Such hydrocarbon-containing fluids include, but are not limited to, light cycle oil, kerosene, straight run diesel, hydrotreated diesel, and the like, and combinations thereof.
The invention is especially suitable for sulfur-containing hydrocarbon oil with higher naphthene content, preferably the sulfur content in the sulfur-containing hydrocarbon oil is 200-1500 ppm, and the naphthene content is 10-30%.
The term "sulfur" as used herein means any form of elemental sulfur such as organosulfur compounds commonly found in hydrocarbon-containing fluids such as cracked-gasoline or diesel fuel. Sulfur present in the hydrocarbon-containing fluid of the present invention includes, but is not limited to, carbon Oxysulfide (COS), carbon disulfide (CS) 2 ) Mercaptans or other thiophenes, and the like, and combinations thereof, including, inter alia, thiophenes, benzothiophenes, alkylthiophenes, alkylbenzothiophenes, and alkyldibenzothiophenes, as well as the higher molecular weight thiophenes commonly found in diesel fuels.
The composition of the hydrocarbon oil desulfurization catalyst provided by the invention contains an alpha-MoC component, which can be favorable for better dispersion of promoter metal, has better interaction with metal and promotes the dehydroaromatization reaction of naphthenes. The catalyst has high desulfurizing activity, obvious octane number improving performance, capacity of producing hydrogen and less hydrogen consumption.
The present invention will be described in detail by examples.
The hydrocarbon oil desulfurization catalysts obtained in examples and comparative examples were subjected to structural measurement by obtaining XRD patterns using an X-ray diffractometer (Siemens company D5005 type), cu target, ka radiation, solid detector, tube voltage 40kV, tube current 40mA;
in the following examples and comparative examples, the composition of the hydrocarbon oil desulfurization catalyst was calculated as a charge.
The specific surface area is determined according to the international test standard ISO-9277 using the nitrogen physisorption BET method. For example, the specific surface area of the support may be measured using a NOVA2000e type nitrogen physical adsorption instrument from Kang Da, U.S.A.
The average particle diameter was calculated from the half-width of the XRD crystal face using the Scherrer formula.
Preparation example 1
Dissolving ammonium heptamolybdate in deionized water, stirring to dissolve completely, evaporating to dryness in an oil bath at 100 ℃, grinding, placing in an oven at 60 ℃ for 3 hours, placing the catalyst in a muffle furnace for calcination, programming to 500 ℃ and keeping for 120 minutes. And then the obtained MoO 3 At a volume ratio of 20% CH 4 /H 2 Carbonizing in the atmosphere of (2), programming to 650 ℃ and keeping for 120min to obtain the pure alpha-MoC with the particle diameter of 12nm and the specific surface area of 50m 2 /g。
Preparation example 2
Sodium molybdate Na 2 MoO 4 Dissolving in deionized water, stirring to dissolve completely, evaporating to dryness in 100deg.C oil bath, grinding, placing in 60deg.C oven for 12 hr, and collecting MoO 3 Calcining in a muffle furnace, programming to 500 ℃ and keeping for 180min. The catalyst is then treated with a catalyst containing 20% by volume of CH 4 /H 2 Carbonizing in the atmosphere of (2), programming to 650 deg.C and maintaining for 300min to obtain pure alpha-MoC with particle diameter of 30nm and specific surface area of 32m 2 /g。
Comparative preparation example
Dissolving ammonium heptamolybdate in a muffle furnace, programming to 500 ℃ and keeping for 240min to obtain MoO 3 . The MoO3 is added in 20% CH 4 /H 2 Carbonizing in the atmosphere of (C), programming to 750 ℃ and keeping for 120min to obtain beta-Mo 2 C, with 0.5% O 2 Passivating the Ar passivation gas for 8 hours to obtain pure beta-phase Mo 2 C。
Example 1
This example illustrates the preparation of the hydrocarbon oil desulfurization catalyst of the present invention.
(1) Preparing a carrier. 4.43kg of zinc oxide powder (Headhorse Co., 99.7% by weight purity) and 6.57kg of deionized water were mixed and stirred for 30 minutes to obtain zinc oxide slurry;
mixing 1.81kg of pseudo-boehmite (catalyst Nanjing division, containing 1.36kg of dry basis) and 2.4kg of alpha-MoC of preparation example 1 with stirring, adding 4.6kg of deionized water, uniformly mixing to obtain slurry, adding 360ml of 30 wt% hydrochloric acid (chemical purity, beijing chemical Co., ltd.) to enable the pH of the slurry to be 2.1, heating to 80 ℃ for aging for 2 hours after stirring and acidification for 1 hour, adding zinc oxide slurry, mixing, and stirring for 1 hour to obtain carrier slurry;
the carrier slurry was subjected to Niro Bowen Nozzle Tower TM Spray drying is carried out by a model spray dryer, the spray drying pressure is 8.5-9.5 MPa, the inlet temperature is below 500 ℃, and the outlet temperature is about 150 ℃. The microspheres obtained by spray drying are dried for 1h at 180 ℃ and then baked for 1h at 635 ℃ to obtain a carrier;
(3) Preparing a catalyst precursor. 3.2kg of a carrier was impregnated with 3.51kg of nickel nitrate hexahydrate (Beijing chemical reagent Co., purity > 98.5 wt%) and 0.6kg of deionized water solution, and the resultant impregnated product was dried at 180℃for 4 hours, and then calcined at 635℃for 1 hour in an air atmosphere to prepare a catalyst precursor;
(4) And (5) reduction. The catalyst precursor was reduced at 425 ℃ for 2 hours in a hydrogen atmosphere to obtain a hydrocarbon oil desulfurization catalyst A1.
The chemical composition of A1 is as follows: the zinc oxide content was 44.3 wt.%, the α -MoC content was 24.0 wt.%, the alumina content was 13.6 wt.%, and the nickel content was 18.1 wt.%.
Example 2
This example illustrates the preparation of the hydrocarbon oil desulfurization catalyst of the present invention.
Pseudo-boehmite 1.56kg (catalyst Nanjing division, containing dry basis 1.17 kg) and 1.80kg of alpha-MoC of preparation example 1 were stirred and mixed, deionized water 8.2kg was added and mixed uniformly to obtain a slurry, 260ml of 30 wt% hydrochloric acid was added to adjust the pH of the slurry to 1.9, and the slurry was stirred and acidified for 1 hour, and then heated to 80 ℃ and aged for 2 hours. After the temperature was lowered, 5.52kg of zinc oxide powder was added and stirred for 1 hour to obtain a carrier slurry.
The hydrocarbon oil desulfurization catalyst A2 was obtained by spray-drying the carrier slurry and introducing nickel as an active component by the method of example 1.
The chemical composition of A2 is as follows: the zinc oxide content was 55.2 wt%, the α -MoC content was 18.0 wt%, the alumina content was 11.7 wt%, and the nickel content was 15.1 wt%.
Example 3
This example illustrates the preparation of the hydrocarbon oil desulfurization catalyst of the present invention.
Mixing 4.93kg of zinc oxide powder, 2.1kg of alpha-MoC of preparation example 1 and 8.8kg of deionized water, and stirring for 30 minutes to obtain a mixed slurry of zinc oxide and alpha-MoC;
mixing pseudoboehmite 1.80kg (obtained from Shandong aluminum factory, dry basis 1.36 kg) and deionized water 4.6kg uniformly to obtain slurry, adding 300ml of 30 wt% hydrochloric acid (obtained from chemical pure, beijing chemical factory) to make pH=2.5, stirring and acidifying for 1 hr, and heating to 80deg.C for aging for 2 hr. And adding the mixed slurry of zinc oxide and alpha-MoC, and stirring for 1h to obtain carrier slurry.
Spray drying of the carrier slurry was carried out in accordance with the method of example 1.
Catalyst precursors and catalysts were prepared by the method of example 1, except that the nickel nitrate and cobalt nitrate solution was used instead of the nickel nitrate hexahydrate impregnated support, the active components nickel and cobalt were introduced, and the hydrocarbon oil desulfurization catalyst A3 was obtained after reduction.
The chemical composition of A3 is as follows: the zinc oxide content was 49.3 wt%, the α -MoC content was 21.0 wt%, the alumina content was 13.5 wt%, the nickel content was 8.1 wt%, and the cobalt content was 8.1 wt%.
Example 4
This example illustrates the preparation of the hydrocarbon oil desulfurization catalyst of the present invention.
4.93kg of zinc oxide powder, 2.1kg of alpha-MoC and 8.8kg of deionized water are mixed and stirred for 30 minutes to obtain a mixed slurry of zinc oxide and alpha-MoC of preparation example 1;
mixing pseudoboehmite 1.80kg (obtained from Shandong aluminum factory, including dry base 1.36 kg) and deionized water 4.6kg uniformly to obtain slurry, adding 300ml of 30 wt% hydrochloric acid to make pH=2.5, stirring and acidifying for 1 hr, heating to 80deg.C, and aging for 2 hr. And adding the mixed slurry of zinc oxide and MoC, and stirring for 1h to obtain carrier slurry.
The hydrocarbon oil desulfurization catalyst A4 was obtained by spray-drying the carrier slurry and introducing nickel as an active ingredient by the method of example 1.
The chemical composition of A4 is as follows: the zinc oxide content was 49.3 wt%, the α -MoC content was 21.0 wt%, the alumina content was 13.5 wt%, and the nickel content was 16.2 wt%.
Example 5
5.02kg of zinc oxide powder (Headhorse Co., 99.7% by weight purity) and 6.17kg of deionized water were mixed and stirred for 30 minutes to obtain zinc oxide slurry;
mixing pseudoboehmite 1.56kg (catalyst Nanjing division, containing dry basis 1.17 kg) and MoC 1.50kg under stirring, adding kaolin 1.08kg (Suzhou Kaolin, containing dry basis 0.8 kg) and deionized water 4.6kg, mixing to obtain slurry, adding hydrochloric acid (chemical purity, beijing chemical Co., ltd.) 30 wt% 360ml to make pH=2.1, acidifying under stirring for 1 hr, heating to 80deg.C, aging for 2 hr, adding zinc oxide slurry, mixing, and stirring for 1 hr to obtain carrier slurry.
The hydrocarbon oil desulfurization catalyst A5 was obtained by spray-drying the carrier slurry and introducing nickel as an active ingredient by the method of example 1.
The chemical composition of A5 is as follows: the zinc oxide content was 50.2 wt%, the α -MoC content was 15.0 wt%, the alumina content was 11.7 wt%, the kaolin content was 8 wt%, and the nickel content was 15.1 wt%.
Comparative example 1
Mixing 4.43kg of zinc oxide powder with 6.57kg of deionized water, and stirring for 30 minutes to obtain zinc oxide slurry;
mixing pseudoboehmite 1.81kg (catalyst Nanjing division, containing dry basis 1.36 kg) and expanded perlite 2.46kg (catalyst Nanjing division, containing dry basis 2.40 kg) under stirring, adding deionized water 4.6kg, mixing uniformly, adding 360ml of 30 wt% hydrochloric acid to make pH=2.1, stirring and acidifying for 1h, heating to 80 ℃ and aging for 2h, adding zinc oxide slurry, mixing, and stirring for 1h to obtain carrier slurry.
The hydrocarbon oil desulfurization catalyst B1 was obtained by spray-drying the carrier slurry and introducing nickel as an active component by the method of example 1.
B1 comprises the following chemical components: the zinc oxide content was 44.3 wt.%, the expanded perlite content was 24.0 wt.%, the alumina content was 13.6 wt.%, and the nickel content was 18.1 wt.%.
Comparative example 2
Taking 1.56kg of pseudo-boehmite (manufactured by Shandong aluminum factory, containing 1.17kg of dry basis) and 1.85kg of diatomite (containing 1.80kg of dry basis), stirring and mixing, adding 8.2kg of deionized water, uniformly mixing, adding 260ml of 30 wt% hydrochloric acid to ensure that the pH of the slurry is=1.9, stirring and acidifying for 1h, and then heating to 80 ℃ and aging for 2h. After the temperature was lowered, 5.52kg of zinc oxide powder was added and stirred for 1 hour to obtain a carrier slurry.
The hydrocarbon oil desulfurization catalyst B2 was obtained by spray-drying the carrier slurry and introducing nickel as an active component by the method of example 1.
B2 comprises the following chemical components: the zinc oxide content was 55.2 wt%, the diatomaceous earth content was 18.0 wt%, the alumina content was 11.7 wt%, and the nickel content was 15.1 wt%.
Comparative example 3
Mixing 4.93kg of zinc oxide powder with 5.57kg of deionized water, and stirring for 30 minutes to obtain zinc oxide slurry;
taking 1.80kg of pseudo-boehmite (manufactured by Shandong aluminum factory, containing 1.35kg of dry basis) and 2.16kg of diatomite (manufactured by world mining company, containing 2.10kg of dry basis), stirring and mixing, adding 4.6kg of deionized water, uniformly mixing, adding 300ml of 30 wt% hydrochloric acid to ensure that the pH of the slurry is=2.5, stirring and acidifying for 1h, and then heating to 80 ℃ for aging for 2h. And adding zinc oxide slurry, mixing, and stirring for 1h to obtain carrier slurry.
The hydrocarbon oil desulfurization catalyst B3 was obtained by spray-drying the carrier slurry and introducing the active components nickel and cobalt by the method of example 3.
B3 comprises the following chemical components: the zinc oxide content was 49.3 wt%, the diatomaceous earth content was 21.0 wt%, the alumina content was 13.5 wt%, the nickel content was 8.1 wt%, and the cobalt content was 8.1 wt%.
Comparative example 4
Mixing 4.93kg of zinc oxide powder with 5.57kg of deionized water, and stirring for 30 minutes to obtain zinc oxide slurry;
mixing pseudoboehmite 1.80kg (obtained from Shandong Alfactory and containing 1.35kg of dry basis) and kaolin 2.84kg (obtained from Suzhou Kaolin factory and containing 2.10kg of dry basis) under stirring, adding deionized water 3.6kg, mixing, adding 300ml of 30 wt% hydrochloric acid to make pH=2.5, stirring, acidifying for 1 hr, and heating to 80deg.C for aging for 2 hr. And adding zinc oxide slurry, mixing, and stirring for 1h to obtain carrier slurry.
Spray drying and molding of the mixed flavor were performed in accordance with the method of example 1, and active component nickel was introduced, followed by reduction to obtain a hydrocarbon oil desulfurization catalyst B4.
B4 comprises the following chemical components: the zinc oxide content was 49.3 wt%, the kaolin content was 21.0 wt%, the alumina content was 13.5 wt%, and the nickel content was 16.2 wt%.
Comparative example 5
4.93kg of zinc oxide powder, 2.1kg of beta-MoC of preparation example 2 and 8.8kg of deionized water are mixed, and the mixture is stirred for 30 minutes to obtain mixed slurry of zinc oxide and beta-MoC;
mixing pseudoboehmite 1.80kg (obtained from Shandong aluminum factory, dry basis 1.36 kg) and deionized water 4.6kg uniformly to obtain slurry, adding 300ml of 30 wt% hydrochloric acid (obtained from chemical pure, beijing chemical factory) to make pH=2.5, stirring and acidifying for 1 hr, and heating to 80deg.C for aging for 2 hr. And adding the mixed slurry of zinc oxide and beta-MoC, and stirring for 1h to obtain carrier slurry.
Spray drying of the carrier slurry was carried out in accordance with the method of example 1.
Catalyst precursors and catalysts were prepared by the method of example 1, except that the nickel nitrate and cobalt nitrate solution was used instead of the nickel nitrate hexahydrate impregnated support, the active components nickel and cobalt were introduced, and the hydrocarbon oil desulfurization catalyst A3 was obtained after reduction.
The chemical composition of A3 is as follows: the zinc oxide content was 49.3 wt%, the beta-MoC content was 21.0 wt%, the alumina content was 13.5 wt%, the nickel content was 8.1 wt%, and the cobalt content was 8.1 wt%.
Example 6
And (5) evaluating desulfurization performance. The desulfurization evaluation experiments were conducted on the hydrocarbon oil desulfurization catalysts A1 to A5 and B1 to B4 by using a fixed bed micro-reaction experimental apparatus, and 16g of the hydrocarbon oil desulfurization catalyst was packed in a fixed bed reactor having an inner diameter of 30mm and a length of 1 m.
The raw material hydrocarbon oil is catalytic cracking gasoline with 780ppm sulfur concentration, the reaction pressure is 1.38MPa, the hydrogen flow is 6.3L/h, the gasoline flow is 80mL/h, the reaction temperature is 410 ℃, and the weight airspeed of the raw material hydrocarbon oil is 4h -1 Desulfurizing the sulfur-containing hydrocarbon oil.
The desulfurization activity is measured by the sulfur content in the gasoline product. The sulfur content in the gasoline product is measured by an off-line chromatographic analysis method by adopting a GC6890-SCD instrument of the Anjeam company.
In order to accurately characterize the activity of the hydrocarbon oil desulfurization catalyst in industrial actual operation, the catalyst after desulfurization evaluation experiment is regenerated in an air atmosphere at 550 ℃. The desulfurization evaluation experiment is carried out on the hydrocarbon oil desulfurization catalyst, the activity of the catalyst is basically stabilized after the catalyst is regenerated for 6 cycles, the sulfur content in the product gasoline after the 6 th cycle stabilization of the catalyst is used for representing the activity of the catalyst, and the sulfur content and the product liquid yield in the product gasoline after the stabilization are shown in a table 1.
The breakthrough sulfur capacities of the hydrocarbon oil desulfurization catalysts A1-A5 and B1-B4 for gasoline desulfurization were calculated and the results are shown in table 1. The breakthrough in the breakthrough sulfur capacity is from the start of gasoline desulfurization to the breakthrough of sulfur content of the obtained gasoline by 10 mug/g. The breakthrough sulfur capacity refers to the total adsorbed sulfur content on the gasoline desulfurization catalyst (based on the total weight of the gasoline desulfurization catalyst) prior to breakthrough.
The Motor Octane Number (MON) and Research Octane Number (RON) of the gasoline before the reaction and after the stabilization of the sixth cycle were measured by GB/T503-1995 and GB/T5487-1995, respectively, and the difference between the two measured values was calculated, and the results are shown in Table 1.
TABLE 1
Note that: the data in the table on octane number is the amount of change in octane number compared to the feed gasoline. "-" means a decrease in octane number as compared to the feed gasoline.
1. The feedstock gasoline had a naphthene content of 26.8%, a sulfur content of 780ppm, a RON of 93.0 and a MON of 82.7.
2. Delta MON represents the added value of product MON;
3. delta RON represents the increased value of RON of the product;
4. delta (RON+MON)/2 is the difference between the antiknock index of the product and the antiknock index of the raw material.
5. The hydrogen amount difference is the difference between the inlet hydrogen amount (Q1) and the outlet hydrogen amount (Q2), and + indicates hydrogen production, -indicates hydrogen consumption.
As can be seen from the data of the results in Table 1, the hydrocarbon oil desulfurization catalyst provided by the invention contains pure alpha-MoC components with specific structures, and can well reduce the sulfur content of gasoline after the hydrocarbon oil desulfurization catalyst is subjected to multiple-cycle desulfurization, so that the catalyst has better desulfurization activity and activity stability, can promote the hydrocarbon oil to carry out dehydrogenation reaction in the desulfurization process, increase the yield of hydrogen, greatly reduce the hydrogen consumption of the catalytic hydrogenation adsorption desulfurization technology, save the cost of hydrocarbon oil desulfurization operation, and improve the octane number of the gasoline product.
Claims (18)
1. A hydrocarbon oil desulfurization catalyst with hydrogen production function, based on the total weight of the catalyst, comprises the following components:
1) 10 to 80 wt% zinc oxide;
2) 3 to 35 wt% of an alumina binder;
3) 5 to 40 wt% of alpha-MoC;
4) 5 to 30 wt% of a metal promoter selected from at least one of cobalt, nickel, iron and manganese.
2. The catalyst according to claim 1, wherein the catalyst comprises, based on the total weight of the catalyst: 40 to 60 weight percent of zinc oxide, 8 to 15 weight percent of alumina binder, 7 to 30 weight percent of alpha-MoC and 12 to 25 weight percent of the metal accelerator.
3. The catalyst according to claim 1 or 2, wherein in the spectrum of the hydrocarbon oil desulfurization catalyst obtained by XRD analysis, there are crystal phase peaks of α -MoC at 2θ=39.6 °, 52.2 °, 62.5 °.
4. Catalyst according to claim 1 or 2, wherein the metal promoter is nickel and/or cobalt.
5. A method of preparing a hydrocarbon oil desulfurization catalyst comprising:
(1) Dissolving molybdate in deionized water, evaporating to remove water, drying, and roasting to obtain MoO 3 A solid; the obtained MoO 3 Carbonizing the solid in a carbonization atmosphere containing a carbon source and hydrogen to obtain alpha-MoC;
(2a) Contacting alpha-MoC, an alumina binder, water and an acidic liquid to form a slurry, and mixing the slurry with zinc oxide to obtain a carrier slurry; or alternatively
(2b) Contacting an alumina binder, water and an acidic liquid to form a slurry, and mixing the slurry with zinc oxide and alpha-MoC to obtain a carrier slurry;
(3) Molding, first drying and first roasting the carrier slurry to obtain a carrier;
(4) Introducing a precursor of a metal promoter into the carrier, and then performing second drying and second roasting to obtain a catalyst precursor;
(5) And reducing the catalyst precursor in a hydrogen atmosphere to obtain the hydrocarbon oil desulfurization catalyst.
6. The method of claim 5, wherein in step (1), the molybdate is selected from the group consisting of sodium molybdate, magnesium molybdate, ammonium heptamolybdate.
7. The method of claim 5, wherein in step (1), the carbonization atmosphere is CH 4 /H 2 Or C 2 H 6 /H 2 The volume ratio of the carbon source to the hydrogen is between 10 and 30 percent.
8. The method according to claim 5, wherein in the step (1), the temperature programmed for carbonization is increased at a rate of 1 to 10 ℃/min, the carbonization temperature is 400 to 800 ℃, and the carbonization time is 60 to 400min.
9. The method according to claim 5, wherein the average particle size of the α -MoC is 1 to 50nm.
10. The method of claim 9, wherein the average particle size of the α -MoC is 5-40 nm.
11. The method of claim 10, wherein the average particle size of the α -MoC is 10-35 nm.
12. The method according to claim 5, wherein the specific surface area of the α -MoC is 5m 2 /g～200m 2 /g。
13. The method according to claim 12, wherein the specific surface area of the a-MoC is 10m 2 /g～150m 2 /g。
14. The method according to claim 13, wherein the specific surface area of the α -MoC is 20 to 80m 2 /g。
15. The method of claim 5, wherein the precursor of the metal promoter is selected from at least one of acetate, carbonate, nitrate, sulfate, thiocyanate, and oxide of the metal promoter.
16. A hydrocarbon oil desulfurization catalyst made by the method of any one of claims 5-15.
17. A process for desulfurizing hydrocarbon oils, comprising: desulfurizing the sulfur-containing hydrocarbon oil with the hydrocarbon oil desulfurizing catalyst of any one of claims 1-4 and 16 at 350-500 deg.c and 0.5-4 MPa in hydrogen atmosphere.
18. The method of claim 17, wherein the sulfur-containing hydrocarbon oil has a sulfur content of 200 to 1500ppm and a naphthene content of 10 to 30%.
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| CN107970941A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil |
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| CN107970941A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | A kind of method of desulfurization of hydrocarbon oil catalyst and preparation method thereof and desulfurization of hydrocarbon oil |
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